Honey - natural or artificial? - Eurofins Scientific · 2020. 7. 28. · Honey Directive 2001/110/EC. Eurofins Firewall Seminar: Honey - natural or artificial? 2 . Annex I - Composition

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Authenticity Honey - natural or artificial?

08.10.2019

Dr Kurt-Peter Raezke

www.eurofins.de


Honey Directive 2001/110/EC

Eurofins Firewall Seminar: Honey - natural or artificial? 2

Annex I - Composition Criteria for Honey “When placed on the market as honey or used in any product intended for human consumption, honey shall not have added to it any food ingredient, including food additives, nor shall any other additions be made other than honey. Honey must, as far as possible, be free from organic or inorganic matters foreign to its composition. … it must not have any foreign tastes, …, have begun to ferment, have an artificially changed acidity or have been heated in such a way that the natural enzymes have been either destroyed or significantly inactivated.”

Annex I – Definition Honey is the natural sweet substance produced by Apis mellifera bees from the nectar of plants or from secretions of living parts of plants or excretions of plant-sucking insects on the living parts of plants, which the bees collect, transform by combining with specific substances of their own, deposit, dehydrate, store and leave in honeycombs to ripen and mature.

https://www.google.de/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=2ahUKEwj_uv6fo__YAhXFZFAKHelSADAQjRx6BAgAEAY&url=https://imker-haseluenne.de.tl/Honig.htm&psig=AOvVaw0itSFB4MGAbMhj-J2LarA6&ust=1517387492317375

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Impact on Honey Authenticity

Responsible to ensure the Quality of Honey

The Beekeeper

good beekeeping practice no foreign smell or tase hive controls humidity colour

The Industry

ensuring safe food certification

supplier management monitoring plans

traceability quality controls

The Laboratory

experiences on products and methods accreditation

Legal Requirements

§ Food Law §

3 Eurofins Firewall Seminar: Honey - natural or artificial?

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Honey Industry: Consumers‘ Awareness

Almost 20 per cent of Australian honey samples

found to not be pure NEWS 3, Oct 2018

‘Honeygate’ deepens as new tests reveal 27% of brands

are adulterated THE CONVERSATION, Oct 2018

Honeygate: How Europe is being flooded with fake

honey THE CAPITALS, Sep 2017

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Supermarkets stung by funny honey adulterated

with sugar and E numbers The Sunday Times, March 2019

Eurofins Firewall Seminar: Honey - natural or artificial?

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Honey Authenticity – Is it Reality?

Stiftung Warentest 30.01.2019

36 honeys were tested:

No adulteration was reported!


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Driving forward analytical improvements & innovations • Improve, harmonise and simplify existing analytical methods • Close current gaps and increase confidence in authenticity testing results

Generation of Market Transparency

With the aim to: Exclude the fraudsters!

By: • Gather more sample information from one analytical test • Providing higher efficiency in terms of short response times, higher sample

throughput and more cost effective tests • Reduce the necessary analytical arsenal and thus simplify the current product

testing recommendations

Our Goals:


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Honey Authenticity

Foresee the unforeseen !

2015: EU Commission Recommendation

ANNEX I Coordinated control plan for honey authenticity

Sampling Strategy (Honey)

Documentary Data

Identity Data Preliminary

Physical Checks

Price


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Honey Authenticity – Documentary Data

THE MANUKA HONEY SCANDAL Simon Usborne, INDIPENDENT, Tuesday 1 July 2014

At the heart of the scandal: basic maths. According to New Zealand's leading manuka association, 1,800 tonnes a year of the honey are now consumed in the UK each year, out of an estimated 10,000 tonnes globally. Yet production of the genuine stuff is set at just 1,700 tonnes, or the equivalent to more than three million small jars. Unless Britain has somehow managed to secure all of it, there's a lot of fake manuka on our shelves.


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Honey Authenticity – Pricing

Production of adulterated Honey

9

9

1000 kg Honey

2,50€ / kg =

2.500 €

1000 kg Adulterated

Honey =

2.300 €

Savings 200 € (8%)

100 kg Syrup

0,50€ / kg = 50,00 €

+

900 kg Honey

2,50€ / L =

2.250 €


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Honey Authenticity – Is it Honey?

E-mail from a manufacturer of sugar syrup: We can offer you the following syrup:

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Syrup passes the following tests NMR EA/LC-IRMS Foreign sugars Foreign enzymes (bFF) ß- and g-amylase SM-B / SM-R / TM-R / Mannose Foreign oligosaccharides Foreign a-amylases (FAmyP) Thermoresistant enzymes geographical origin confirmation

You can mix it 50% with your honey (at least)

40% admixture passes all available tests


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Honey Authenticity – Where are we today?

Still some adulterations cannot be detected It is common to produce tailor-made syrups customised to the honey type and the

specification requirements NMR is good for non-target screening, but not the most sensitive method in all cases:

isotopic and specific marker methods still necessary, tailor-made syrups can pass with up to 40%!

With all the different methods, it is too expensive to always apply them all It is difficult to safely recommend risk-based testing schemes depending on the origin of

the honey (you cannot be sure about that!)

How can we reduce the number of necessary tests and ensure reasonable detection limits for known and perhaps yet unknown adulterations?

11

In 2017 Eurofins introduced LC-Orbitrap-HRMS

for honey adulteration detection

Accredited since

Oct/2018


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Advantages of High Resolution MS

• High Resolution (HR) means of separating mass fragments at the fifth decimal place (exact mass) where previous instrumentation was limited to single-digit mass unit.

• HR measures the ability to distinguish two peaks of slightly different m/z ratios is necessary to separate signals of one compound from those of another.

• HR narrows down the possible chemical formulas of an unknown compound

342 4215

342.1 274

342.11 83

342.116 24

342.1162 8

342.11621 1

Possible chemical formulars for sucrose C12H22O11 m/z 342.11621

Increase in mass resolution

Decrease of possible chemical formulas


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Fingerprint

of the syrups

-5 0 5 10

Log2 Fold Change

0

2

4

6

8

10

12

14

-Log

10 P

-val

ue

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Non-target profiling of the syrup to identify suitable markers (untargeted)

Typical honey compounds

Cross-check with authentic honeys for absence of identified markers (targeted)

Targeted multiclass adulteration marker monitoring (targeted)

Honey-Profiling by LC-Orbitrap-HRMS Building up a syrup database

Typical sugar syrup compounds


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• Ultimate tool, to detect tailor-made syrup addition to honey that cannot be detected by “traditional” methods.

• Future-proof - New syrups can easily be added to the syrup database, in case fraudsters produce “new syrups”.

• Retrospective evaluation of newly discovered adulteration markers in previously measured samples.

• Multiclass adulteration marker screening

Universal markers for all kinds of sugar syrups

Specific markers for individual syrups SM-B, DFA, SM-R, Hf-OS (DP9-18)

• Very sensitive / Threshold LOD for routine application: 5%

Pros of Honey-Profiling by LC-HRMS


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FAQs about LC-HRMS

1. Is the method applicable for all honey from every region and variety? Yes! We do have a syrup database, we do not need a honey database of known geographical origins or botanical varieties. 2. Can you detect sugar syrup adulteration, when the syrups is not in the

database? Properly yes. We do have universal markers, and a lot of syrups share the same marker compounds. It is very unlikely, that a syrup will not contain any of the >400 already identified markers. However, when we include the syrups into our database, this will improve the LOQ.

3. Can you determine the source of the syrup which is in the honey? Not all syrups that we have in our database are of known source or origin. 4. Can you quantify the amount of syrup in the honey?

Not accurately, because the concentration of the marker compounds are different between the syrups. Therefore, we can only estimate the amount based on experiences.


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Honey Authenticity – SOTA

State-Of-The-Art Approach 2019: 13C EA/LC-IRMS + NMR Profiling + LC-HRMS

+ Pollen/Sensory (Type/Origin)

Sources: https://www.eurofins.de/food-analysis/food-news/food-testing-news/lc-hrms-authenticity-analysis-of-honey/ https://ec.europa.eu/jrc/sites/jrcsh/files/ares181569074-1_technical_round_table_on_honey_adulteration_report.pdf

Capabilities: 13C EA/LC-IRMS NMR Profiling LC-HRMS Pollen Sensory

C4 Sugars C3 Sugars Tailor-made Syrups Illegal Processing R&D Moisture Reduction not in scope Type/Origin Verification R&D


https://www.eurofins.de/food-analysis/food-news/food-testing-news/lc-hrms-authenticity-analysis-of-honey/





















https://ec.europa.eu/jrc/sites/jrcsh/files/ares181569074-1_technical_round_table_on_honey_adulteration_report.pdf




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Honey Authenticity – Recommendation

Future honey authenticity testing will include:


LC-HRMS (can be used as screening and conformation method, no separate confirmation necessary, less database requirements)

Stable Isotopes (EA/LC-IRMS, closest to standardisation)

NMR (fast screening, needs to be continuously improved by database extension and harmonisation; however, confirmation of non-conform results by other methods necessary)

And still: Microscopy (pollen, particles typical for adulteration) / Sensory

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Honey Authenticity: Conclusion

Currently no single method is available ensure food authenticity and to detect adulterated food!

Prevention and fighting against prevalence of fraudulent practices will result in an increase on:

Fair Trade Authentic Food

Food Safety Consumer Confidence


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Thank you for your attention


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Contact

Eurofins Food Integrity Control Services Berliner Str. 2 27721 Ritterhude Germany T: +49 4292 4077 210 E: [email protected]

Dr Kurt-Peter Raezke


mailto:[email protected]

Documents

Honey - natural or artificial? - Eurofins Scientific · 2020. 7. 28. · Honey Directive 2001/110/EC. Eurofins Firewall Seminar: Honey - natural or artificial? 2 . Annex I - Composition